Method and apparatus for drying carboxylic acid

ABSTRACT

Disclosed is a method and apparatus for drying a wet cake in a carboxylic acid production process. The method comprises employing a contact dryer for drying solid particles of carboxylic acid, where the solid particles can have a residence time of less than about 7 minutes in the dryer and an exit temperature of less than about 250° C. upon exiting the dryer.

RELATED APPLICATIONS

This application claims the priority benefit of U.S. Provisional Pat.App. Ser. Nos. 60/777,906 and 60/777,908, both filed Mar. 1, 2006, theentire disclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to a drying process for use inthe production of a carboxylic acid. More specifically, the presentinvention concerns a method for drying solid particles of terephthalicacid in a drying zone where the residence time of the solid particles inthe drying zone is reduced and the exit temperature of the solidparticles is less than about 250° C.

2. Description of the Prior Art

In conventional crude terephthalic acid (CTA) production processes,para-xylene undergoes oxidation to form CTA particles. The CTA particlesare then typically subjected to isolation and washing. In a conventionalpurified terephthalic acid (PTA) production process, an additional stepis employed where the CTA particles are purified prior to theisolation/washing step. In either a CTA or a PTA production process, theterephthalic acid (TPA) particles exiting the isolation/washing step aretypically in the form of a wet cake. In some TPA production processes,the wet cake is then dried in a dryer to thereby produce a substantiallydry TPA product.

Various methods are known in the art for drying a TPA product. Suchmethods include the use of a rotary dryer, as well as drying the TPA wetcake by contacting it with a flow of inert gas, which can be achieved ina fluid bed dryer, a ring dryer, or in a solids conveying system.However, conventional methods for drying TPA can cause significantproduct degradation and/or sublimation, both of which are undesirable.Accordingly, there is a need for methods and/or equipment that canminimize product degradation and/or sublimation when drying a TPAproduct.

SUMMARY OF THE INVENTION

One embodiment of the present invention concerns a method for dryingsolid particles comprising a carboxylic acid. The method of thisembodiment comprises: (a) introducing a wet cake comprising the solidparticles into a contact dryer comprising an inner surface; and (b)drying the wet cake in the contact dryer to thereby produce asubstantially dry product comprising at least a portion of the solidparticles, wherein at least about 10 percent of the solid particles forma layer over at least a portion of the inner surface, wherein the layerhas an average thickness of less than about 1.5 inches, wherein thesolid particles have an exit temperature of less than about 250° C. uponexiting the dryer.

Another embodiment of the present invention concerns a method forproducing a substantially dry crude terephthalic acid (CTA) particulateproduct. The method of this embodiment comprises: (a) oxidizing anaromatic compound in an oxidation zone to thereby produce a slurrycomprising solid CTA particles; (b) treating at least a portion of theslurry in a product isolation zone to thereby produce a wet cakecomprising at least a portion of the solid CTA particles; and (c) dryingat least a portion of the wet cake in a contact dryer comprising aninner surface to thereby produce the substantially dry CTA particulateproduct, wherein at least about 10 percent of the solid CTA particlesform a layer over at least a portion of the inner surface, wherein thelayer has an average thickness of less than about 1.5 inches, whereinthe solid CTA particles have an exit temperature of less than about 250°C. upon exiting the dryer.

Yet another embodiment of the present invention concerns a method fordrying a wet cake comprising terephthalic acid (TPA). The method of thisembodiment comprises: (a) introducing the wet cake into a contact dryer;and (b) drying the wet cake in the dryer to thereby produce a dry TPAproduct, wherein, during drying, at least a portion of the TPA in thewet cake forms a thin layer on the inside surface of the dryer, whereinthe dry TPA product has a temperature in the range of from about 105 toabout 240° C. upon exiting the dryer.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

A preferred embodiment of the present invention is described in detailbelow with reference to the attached drawing figures, wherein:

FIG. 1 is a process flow diagram illustrating a system for theproduction, purification, and drying of carboxylic acid constructed inaccordance with the present invention, particularly illustrating aconfiguration where the crude slurry from the oxidation reactor issubjected to purification, the resulting purified slurry is subjected toproduct isolation, and the wet cake from the product isolation zone issubjected to drying in a drying zone;

FIG. 2 is a side view of a dryer that may be used in one embodiment ofthe present invention with certain sections being cut away to moreclearly illustrate the operation of the dryer;

FIG. 3 is a sectional view of the dryer taken along line 3-3 in FIG. 2,particularly illustrating a rotor having a plurality of radial armsaffixed thereto and paddles attached to each individual radial arm;

FIG. 4 is a weight percent vs. time plot depicting the thermalgravimetric analyses of purified terephthalic acid (PTA) in air, PTA innitrogen, crude terephthalic acid (CTA) in air, and CTA in nitrogen,determined in accordance with the procedure described in Example 5; and

FIG. 4 a is a magnified view of the plot depicted in FIG. 4,particularly illustrating the weight percent range from 95 to 100 andthe time range from 185 to 285 of the weight percent vs. time plotdepicted in FIG. 4.

DETAILED DESCRIPTION

FIG. 1 illustrates an embodiment of the present invention wherecarboxylic acid produced in an oxidation reactor and purified in apurification reactor is subjected to product isolation. A portion of theresulting wet cake from the product isolation zone is treated in adrying zone to thereby produce a substantially dry carboxylic acidparticulate product. Various embodiments of the drying zone aredescribed in more detail below with reference to FIGS. 2 and 3.

In the embodiment illustrated in FIG. 1, a predominately fluid-phasefeed stream containing an oxidizable compound (e.g., para-xylene), asolvent (e.g., acetic acid and/or water), and a catalyst system (e.g.,cobalt, manganese, and/or bromine) can be introduced into oxidation zone10. A predominately gas-phase oxidant stream containing molecular oxygencan also be introduced into oxidation zone 10. The fluid- and gas-phasefeed streams form a multi-phase reaction medium in oxidation zone 10.The oxidizable compound can undergo partial oxidation in a liquid phaseof the reaction medium contained in oxidation zone 10.

In one embodiment of the present invention, oxidation zone 10 cancomprise an agitated reactor. Agitation of the reaction medium inoxidation zone 10 can be provided by any means known in the art. As usedherein, the term “agitation” shall denote work dissipated into thereaction medium causing fluid flow and/or mixing. In one embodiment,oxidation zone 10 can be a mechanically-agitated reactor equipped withmeans for mechanically agitating the reaction medium. As used herein,the term “mechanical agitation” shall denote agitation of the reactionmedium caused by physical movement of a rigid or flexible element(s)against or within the reaction medium. For example, mechanical agitationcan be provided by rotation, oscillation, and/or vibration of internalstirrers, paddles, vibrators, or acoustical diaphragms located in thereaction medium. In another embodiment of the present invention,oxidation zone 10 can comprise a bubble column reactor. As used herein,the term “bubble column reactor” shall denote a reactor for facilitatingchemical reactions in a multi-phase reaction medium, wherein agitationof the reaction medium is provided primarily by the upward movement ofgas bubbles through the reaction medium. As used herein, the terms“majority,” “primarily,” and “predominately” shall mean more than 50percent.

The oxidizable compound present in the fluid-phase feed streamintroduced into oxidation zone 10 can comprise at least one hydrocarbylgroup. Also, the oxidizable compound can comprise an aromatic compound.In one embodiment, the oxidizable compound can comprise an aromaticcompound with at least one attached hydrocarbyl group or at least oneattached substituted hydrocarbyl group or at least one attachedheteroatom or at least one attached carboxylic acid function (—COOH). Inanother embodiment, the oxidizable compound can comprise an aromaticcompound with at least one attached hydrocarbyl group or at least oneattached substituted hydrocarbyl group with each attached groupcomprising from 1 to 5 carbon atoms. In yet another embodiment, theoxidizable compound can be an aromatic compound having exactly twoattached groups with each attached group comprising exactly one carbonatom and consisting of methyl groups and/or substituted methyl groupsand/or at most one carboxylic acid group. Suitable examples of theoxidizable compound include, but are not limited to, para-xylene,meta-xylene, para-tolualdehyde, meta-tolualdehyde, para-toluic acid,meta-toluic acid, and/or acetaldehyde. In one embodiment of the presentinvention, the oxidizable compound comprises para-xylene.

A “hydrocarbyl group,” as defined herein, is at least one carbon atomthat is bonded only to hydrogen atoms and/or to other carbon atoms. A“substituted hydrocarbyl group,” as defined herein, is at least onecarbon atom bonded to at least one heteroatom and to at least onehydrogen atom. “Heteroatoms,” as defined herein, are all atoms otherthan carbon and hydrogen atoms. “Aromatic compounds,” as defined herein,comprise an aromatic ring and can comprise at least 6 carbon atoms andcan also comprise only carbon atoms as part of the ring. Suitableexamples of such aromatic rings include, but are not limited to,benzene, biphenyl, terphenyl, naphthalene, and other carbon-based fusedaromatic rings.

The amount of oxidizable compound present in the fluid-phase feed streamintroduced into oxidation zone 10 can be in the range of from about 4 toabout 20 weight percent, or in the range of from 6 to 15 weight percent.

The solvent present in the fluid-phase feed stream introduced intoprimary oxidation reactor 10 can comprise an acid component and a watercomponent. The solvent can be present in the fluid-phase feed stream ata concentration in the range of from about 60 to about 98 weightpercent, in the range of from about 80 to about 96 weight percent, or inthe range of from 85 to 94 weight percent. The acid component of thesolvent can be an organic low molecular weight monocarboxylic acidhaving from 1 to 6 carbon atoms, or 2 carbon atoms. In one embodiment,the acid component of the solvent can comprise acetic acid. The acidcomponent can make up at least about 75 weight percent of the solvent,at least about 80 weight percent of the solvent, or in the range of from85 to 98 weight percent of the solvent, with the balance being water.

As mentioned above, the fluid-phase feed stream introduced intooxidation zone 10 can also include a catalyst system. The catalystsystem can be a homogeneous, liquid-phase catalyst system capable ofpromoting at least partial oxidation of the oxidizable compound. Also,the catalyst system can comprise at least one multivalent transitionmetal. In one embodiment, the catalyst system can comprise cobalt,bromine, and/or manganese.

When cobalt is present in the catalyst system, the fluid-phase feedstream can comprise cobalt in an amount such that the concentration ofcobalt in the liquid phase of the reaction medium is maintained in therange of from about 300 to about 6,000 parts per million by weight(ppmw), in the range of from about 700 to about 4,200 ppmw, or in therange of from 1,200 to 3,000 ppmw. When bromine is present in thecatalyst system, the fluid-phase feed stream can comprise bromine in anamount such that the concentration of bromine in the liquid phase of thereaction medium is maintained in the range of from about 300 to about5,000 ppmw, in the range of from about 600 to about 4,000 ppmw, or inthe range of from 900 to 3,000 ppmw. When manganese is present in thecatalyst system, the fluid-phase feed stream can comprise manganese inan amount such that the concentration of manganese in the liquid phaseof the reaction medium is maintained in the range of from about 20 toabout 1,000 ppmw, in the range of from about 40 to about 500 ppmw, or inthe range of from 50 to 200 ppmw.

In one embodiment of the present invention, cobalt and bromine can bothbe present in the catalyst system. The weight ratio of cobalt to bromine(Co:Br) in the catalyst system can be in the range of from about 0.25:1to about 4:1, in the range of from about 0.5:1 to about 3:1, or in therange of from 0.75:1 to 2:1. In another embodiment, cobalt and manganesecan both be present in the catalyst system. The weight ratio of cobaltto manganese (Co:Mn) in the catalyst system can be in the range of fromabout 0.3:1 to about 40:1, in the range of from about 5:1 to about 30:1,or in the range of from 10:1 to 25:1.

During oxidation, the oxidizable compound (e.g., para-xylene) can becontinuously introduced into oxidation zone 10 at a rate of at leastabout 5,000 kilograms per hour, at a rate in the range of from about10,000 to about 80,000 kilograms per hour, or in the range of from20,000 to 50,000 kilograms per hour. During oxidation, the ratio of themass flow rate of the solvent to the mass flow rate of the oxidizablecompound entering oxidation zone 10 can be maintained in the range offrom about 2:1 to about 50:1, in the range of from about 5:1 to about40:1, or in the range of from 7.5:1 to 25:1.

The predominately gas-phase oxidant stream introduced into oxidationzone 10 can comprise in the range of from about 5 to about 40 molepercent molecular oxygen, in the range of from about 15 to about 30 molepercent molecular oxygen, or in the range of from 18 to 24 mole percentmolecular oxygen. The balance of the oxidant stream can be comprisedprimarily of a gas or gases, such as nitrogen, that are inert tooxidation. In one embodiment, the oxidant stream consists essentially ofmolecular oxygen and nitrogen. In another embodiment, the oxidant streamcan be dry air that comprises about 21 mole percent molecular oxygen andabout 78 to about 81 mole percent nitrogen. In an alternative embodimentof the present invention, the oxidant stream can comprise substantiallypure oxygen.

During liquid-phase oxidation in oxidation zone 10, the oxidant streamcan be introduced into oxidation zone 10 in an amount that providesmolecular oxygen somewhat exceeding the stoichiometric oxygen demand.Thus, the ratio of the mass flow rate of the oxidant stream (e.g., air)to the mass flow rate of the oxidizable compound (e.g., para-xylene)entering oxidation zone 10 can be maintained in the range of from about0.5:1 to about 20:1, in the range of from about 1:1 to about 10:1, or inthe range of from 2:1 to 6:1.

The liquid-phase oxidation reaction carried out in oxidation zone 10 canbe a precipitating reaction that generates solids. In one embodiment,the liquid-phase oxidation carried out in oxidation zone 10 can cause atleast about 10 weight percent of the oxidizable compound (e.g.,para-xylene) introduced into oxidation zone 10 to form solids (e.g.,crude terephthalic acid (CTA) particles) in the reaction medium. Inanother embodiment, the liquid-phase oxidation carried out in oxidationzone 10 can cause at least about 50 weight percent of the oxidizablecompound (e.g., para-xylene) introduced into oxidation zone 10 to formsolids (e.g., CTA particles) in the reaction medium. In yet anotherembodiment, the liquid-phase oxidation carried out in oxidation zone 10can cause at least about 90 weight percent of the oxidizable compound(e.g., para-xylene) introduced into oxidation zone 10 to form solids(e.g., CTA particles) in the reaction medium. In one embodiment, thesolids content of the reaction medium can be maintained in the range offrom about 5 to about 40 weight percent, in the range of from about 10to about 35 weight percent, or in the range of from 15 to 30 weightpercent. As used herein, the term “solids content” shall denote theweight percent solids in a multi-phase mixture.

During oxidation in oxidation zone 10, the multi-phase reaction mediumcan be maintained at an elevated temperature in the range of from about125 to about 200° C., in the range of from about 150 to about 180° C.,or in the range of from 155 to 165° C. The overhead pressure inoxidation zone 10 can be maintained in the range of from about 1 toabout 20 bar gauge (barg), in the range of from about 2 to about 12barg, or in the range of from 4 to 8 barg.

In the embodiment of FIG. 1, a crude slurry can be withdrawn from anoutlet of oxidation zone 10 via line 12. The solid phase of the crudeslurry in line 12 can be formed primarily of solid particles of CTA. Theliquid phase of the crude slurry in line 12 can be a liquid motherliquor comprising at least a portion of the solvent, one or morecatalyst components, and minor amounts of dissolved terephthalic acid(TPA). The solids content of the crude slurry in line 12 can be the sameas the solids content of the reaction medium in oxidation zone 10,discussed above.

In one embodiment of the present invention, the crude slurry in line 12can comprise impurities. As used herein, the term “impurities” isdefined as any substance other than TPA, solvent, catalyst, and water.Such impurities can include oxidation byproducts formed during the atleast partial oxidation of the above-mentioned oxidizable compound(e.g., para-xylene) including, but not limited to, benzoic acid (BA),bromo-benzoic acid, bromo-acetic acid, isophthalic acid, trimelliticacid, 2,5,4′-tricarboxybiphenyl, 2,5,4′-tricarboxybenzophenone,para-toluic acid (p-TAc), 4-carboxybenzaldehyde (4-CBA),monocarboxyfluorenones, monocarboxyfluorenes, and/ordicarboxyfluorenones.

Subsequent to removal from oxidation zone 10, the crude slurry canoptionally be introduced into purification zone 14 via line 12. In oneembodiment, the crude slurry can be treated in purification zone 14 suchthat the concentration of at least one of the above-mentioned impuritiesin the crude slurry is reduced, thereby producing a purified slurry.Such reduction in the concentration of impurities in the TPA can beaccomplished by oxidative digestion, hydrogenation, and/ordissolution/recrystallization.

In one embodiment of the present invention, the crude slurry fed topurification zone 14 can have a 4-CBA content of at least about 100parts per million based on the weight of the solids in the crude slurry(ppmw_(cs)), in the range of from about 200 to about 10,000 ppmw_(cs),or in the range of from 800 to 5,000 ppmw_(cs). The crude slurry fed topurification zone 14 can have a p-TAc content of at least about 250ppmw_(cs), in the range of from about 300 to about 5,000 ppmw_(cs), orin the range of from 400 to 1,500 ppmw_(cs). The purified slurry exitingpurification zone 14 can have a 4-CBA content of less than about 150parts per million based on the weight of the solids in the purifiedslurry (ppmw_(ps)), less than about 100 ppmw_(ps), or less than 50ppmw_(ps). The purified slurry exiting purification zone 14 can have ap-TAc content of less than about 300 ppmw_(ps), less than about 200ppmw_(ps), or less than 150 ppmw_(ps). In one embodiment, treatment ofthe crude slurry in purification zone 14 can cause the purified slurryexiting purification zone 14 to have a 4-CBA and/or p-TAc content thatis at least about 50 percent less than the 4-CBA and/or p-TAc content ofthe crude slurry fed to purification zone 14, at least about 85 percentless, or at least 95 percent less. By way of illustration, if the 4-CBAcontent of the crude slurry fed to purification zone 14 is 200 ppmw_(cs)and the 4-CBA content of the purified slurry exiting purification zone14 is 100 ppmw_(ps), then the 4-CBA content of the purified slurry is 50percent less than the 4-CBA content of the crude slurry.

In one embodiment of the present invention, the crude slurry can besubjected to purification by oxidative digestion in purification zone14. As used herein, the term “oxidative digestion” denotes a processstep or steps where a feed comprising solid particles is subjected tooxidation under conditions sufficient to permit oxidation of at least aportion of the impurities originally trapped in the solid particles.Purification zone 14 can comprise one or more reactors or zones. In oneembodiment, purification zone 14 can comprise one or moremechanically-agitated reactors. A secondary oxidant stream, which canhave the same composition as the gas-phase oxidant stream fed tooxidation zone 10 discussed above, can be introduced into purificationzone 14 to provide the molecular oxygen required for oxidativedigestion. Additional oxidation catalyst can be added if necessary. Inan alternative embodiment of the present invention, a stream comprisinghydrogen can be introduced into purification zone 14 for hydrogenationof the crude slurry.

When oxidative digestion is employed in purification zone 14, thetemperature at which oxidative digestion is carried out can be at leastabout 10° C. greater than the temperature of oxidation in oxidation zone10, in the range of from about 20 to about 80° C. greater, or in therange of from 30 to 50° C. greater. The additional heat required for theoperation of purification zone 14 can be provided by supplying avaporized solvent to purification zone 14 and allowing the vaporizedsolvent to condense therein. The oxidative digestion temperature inpurification zone 14 can be maintained in the range of from about 180 toabout 240° C., in the range of from about 190 to about 220° C., or inthe range of from 200 to 210° C. The oxidative digestion pressure inpurification zone 14 can be maintained in the range of from about 100 toabout 350 pounds per square inch gauge (psig), in the range of fromabout 175 to about 275 psig, or in the range of from 185 to 225 psig.

In one embodiment of the present invention, purification zone 14 caninclude two digestion reactors/zones—an initial digester and a finaldigester. When purification zone 14 includes an initial digester and afinal digester, the final digester can be operated at a lowertemperature and pressure than the initial digester. In one embodiment,the operating temperature of the final digester can be at least about 2°C. lower than the operating temperature of the initial digester, or inthe range of from about 5 to about 15° C. lower than the operatingtemperature of the initial digester. In one embodiment, the operatingpressure of the final digester can be at least about 5 psig lower thanthe operating pressure of the initial digester, or in the range of fromabout 10 to about 50 psig lower than the operating pressure of theinitial digester. The operating temperature of the initial digester canbe in the range of from about 195 to about 225° C., in the range of from205 to 215° C., or about 210° C. The operating pressure of the initialdigester can be in the range of from about 215 to about 235 psig, orabout 225 psig. The operating temperature of the final digester can bein the range of from about 190 to about 220° C., in the range of from200 to 210° C., or about 205° C. The operating pressure of the finaldigester can be in the range of from about 190 to 210 psig, or about 200psig.

In one embodiment of the present invention, purification zone 14 cancomprise optional first and second solvent swap zones. Optional firstand second solvent swap zones can operate to replace at least a portionof the existing solvent in a slurry with a replacement solvent.Equipment suitable for such replacement includes, but is not limited to,a decanter centrifuge followed by a reslurry with replacement solvent, adisc stack centrifuge, an advancing front crystallizer, or multipledecanter centrifuges with optional counter current washing. Thereplacement oxidation solvent can have substantially the samecomposition as the solvent introduced into oxidation zone 10, asdescribed above.

In one embodiment, the crude slurry fed to purification zone 14 can betreated in the optional first solvent swap zone prior to purification ofthe crude slurry by the above-mentioned oxidative digestion. In anotherembodiment, a purified slurry resulting from oxidative digestion of thecrude slurry can be treated in the optional second solvent swap zone.

Optionally, at least a portion of the displaced oxidation solvent fromthe optional first and/or second solvent swap zones can be dischargedfrom purification zone 14. In one embodiment, at least a portion of thedisplaced oxidation solvent can be routed to oxidation zone 10.

In another embodiment of the present invention, purification zone 14 cancomprise an optional crystallization zone and/or an optional coolingzone. A purified slurry resulting from the above-mentioned oxidativedigestion of the crude slurry can be treated in the optionalcrystallization zone to at least partially increase the particle sizedistribution of the purified slurry. Optional crystallization zone cancomprise any equipment known in the art that can operate to increase theparticle size distribution of the purified slurry. When an optionalcooling zone is employed, the purified slurry can be cooled therein to atemperature in the range of from about 20 to about 195° C. When both acrystallization zone and a cooling zone are employed, the purifiedslurry can be treated first in the crystallization zone and subsequentlyin the cooling zone.

Referring again to FIG. 1, a purified slurry can be withdrawn from anoutlet of purification zone 14 via line 16. The solid phase of thepurified slurry can be formed primarily of purified terephthalic acid(PTA) particles, while the liquid phase can be formed of a motherliquor. The solids content of the purified slurry in line 16 can be inthe range of from about 5 to about 40 weight percent, in the range offrom about 10 to about 35 weight percent, or in the range of from 15 to30 weight percent. The purified slurry in line 16 can be introduced intoproduct isolation zone 18 for at least partial recovery of the solid PTAparticles.

Optionally, at least a portion of the crude slurry in line 12 can beintroduced into product isolation zone 18 via line 12 a. As mentionedabove, the solid phase of the crude slurry can be formed primarily ofCTA particles, while the liquid phase can be formed of a mother liquor.The solids content of the crude slurry in line 12 a can be in the rangeof from about 5 to about 40 weight percent, in the range of from about10 to about 35 weight percent, or in the range of from 15 to 30 weightpercent. The crude slurry in line 12 a can be introduced into productisolation zone 18 for recovery of the solid CTA particles.

Product isolation zone 18 can separate the crude slurry and/or thepurified slurry into a predominately fluid phase mother liquor and a wetcake. Product isolation zone 18 can comprise any method of solid/liquidseparation known in the art that is capable of generating a wet cake anda mother liquor stream. In addition, it may be desirable for productisolation zone 18 to have the capability of washing the wet cake.Suitable equipment for use in product isolation zone 18 includes, but isnot limited to, a pressure drum filter, a vacuum filter, a vacuum drumfilter, a vacuum belt filter, multiple solid bowl centrifuges withoptional counter current wash, or a perforated centrifuge.

In one embodiment of the present invention, a wash stream can beintroduced into product isolation zone 18 to wash at least a portion ofthe wet cake generated in product isolation zone 18, thereby producing awashed wet cake. In one embodiment, the wash stream can comprise aceticacid and/or water. Optionally, after washing the wet cake, the used washliquor can be withdrawn from product isolation zone 18, and at least aportion of the wash liquor can be routed, either directly or indirectly,to oxidation zone 10.

The above-mentioned wet cake generated in product isolation zone 18 canbe discharged via line 20. In one embodiment of the present invention,the wet cake generated in product isolation zone 18 can primarilycomprise solid particles of carboxylic acid. In one embodiment, thecarboxylic acid can be an aromatic dicarboxylic acid, which can be solidTPA particles. The solid TPA particles can comprise CTA and/or PTAparticles. In one embodiment, the solid particles can have a meanparticle size in the range of from about 1 to about 500 μm, in the rangeof from about 10 to about 350 μm, or in the range of from 20 to 200 μm.

In one embodiment of the present invention, the wet cake can comprise inthe range of from about 2 to about 25 weight percent liquid, in therange of from about 4 to about 20 weight percent liquid, or in the rangeof from 6 to 15 weight percent liquid. Additionally, the wet cake inline 20 can comprise oxidation byproducts, as discussed above.Furthermore, the wet cake in line 20 can comprise acetic acid and/orwater.

In one embodiment of the present invention, the wet cake in line 20 canbe introduced into drying zone 100 via line 20. The wet cake in line 20can be fed to drying zone 100 at a rate of at least about 20 pounds perhour per square foot (lbs/hr/ft²) of the inner surface area of dryingzone 100. In another embodiment, the wet cake in line 20 can be fed todrying zone 100 at a feed rate of at least about 35 lbs/hr/ft², or inthe range of from about 40 to about 175 lbs/hr/ft². The wet cake in line20 can have an inlet temperature in the range of from about 0 to about220° C., in the range of from about 20 to about 200° C., in the range offrom about 40 to about 150° C., in the range of from about 60 to about120° C., or in the range of from 65 to 105° C. upon entering drying zone100. As used herein, the term “inlet temperature” is defined as thetemperature of the wet cake immediately upon being introduced intodrying zone 100.

Drying zone 100 can operate to produce a substantially dry TPAparticulate product comprising solid TPA particles. As used herein, theterm “substantially dry” is defined as a product comprising less thanabout 2 weight percent liquid. In another embodiment of the presentinvention, the substantially dry TPA particulate product can compriseless than about 1 weight percent liquid, less than about 0.5 weightpercent liquid, less than about 0.2 weight percent liquid, or less than0.1 weight percent liquid.

In one embodiment, at least a portion of the vapor produced from theliquid removed from the solid TPA particles can be removed from dryingzone 100 via line 22. The vapor in line 22 can comprise solvent asdescribed above in relation to the solvent contained in the fluid-phasefeed stream fed to oxidation zone 10 (e.g., acetic acid and/or water).

Referring still to FIG. 1, in one embodiment of the present invention,vacuum source 24 can be used to create vacuum conditions in drying zone100. During drying operations, drying zone 100 can be operated at apressure in the range of from about 50 to about 750 torr, in the rangeof from about 100 to about 700 torr, or in the range of from 150 to 650torr. In another embodiment, vacuum source 24 can also operate to createvacuum conditions in product isolation zone 18, such that productisolation zone 18 and drying zone 100 share vacuum source 24. In anotherembodiment, a condenser (not depicted) can be disposed substantiallybetween drying zone 100 and vacuum source 24. The condenser can operateto condense at least a portion of the vapor in line 22.

In one embodiment of the present invention, the solid particles can havean average residence time in drying zone 100 of less than about 7minutes, less than about 5 minutes, less than about 3 minutes, less thanabout 2 minutes, or less than 1 minute. As used herein, the term“residence time” is defined as the difference in time between theintroduction of a solid particle into drying zone 100 via line 20 andthe time when that same solid particle exits the drying zone via line26.

In another embodiment of the present invention, the solid particles havea measurable exit temperature upon being withdrawn from drying zone 100via line 26. In one embodiment, the solid particles can have an exittemperature of less than about 250° C., in the range of form about 105to about 240° C., in the range of from about 110 to about 200° C., inthe range of from about 115 to about 175° C., or in the range of from120 to 160° C. As used herein, the term “exit temperature” is defined asthe temperature of the solid particles immediately upon exiting dryingzone 100 (e.g., upon introduction into line, 26). Additionally, the exittemperature of the solid particles can be at least about 25° C. greater,at least about 50° C. greater, or at least 100° C. greater than theinlet temperature of the wet cake as discussed above.

In one embodiment of the present invention, the solid particles exitingdrying zone 100 via line 26 can pass through vacuum seal 28. Vacuum seal28 can operate to allow solid particles to be withdrawn from drying zone100 while at least partially maintaining the pressure in drying zone100. In one embodiment, vacuum seal 28 can maintain the pressure indrying zone 100 such that, upon withdrawal of solid particles, thepressure change in drying zone 100 is less than about 20 percent, lessthan about 10 percent, or less than 5 percent. Vacuum seal 28 can be anyvacuum seal device that can at least partially maintain the pressure indrying zone 100 while allowing the withdrawal of solids. An example of asuitable device that can be used for vacuum seal 28 includes, but is notlimited to, a rotary air lock valve.

In one embodiment of the present invention, drying zone 100 can comprisean inert atmosphere during drying operations. As used herein, the term“inert atmosphere” is defined as an atmosphere that is substantiallynon-reactive in the processes of the present invention. Such an inertatmosphere can be achieved by introducing an inert gas into drying zone100. Any method known in the art for introducing a gas into a vessel canbe employed to introduce the inert gas into drying zone 100. In oneembodiment, introduction of the inert gas can be achieved by allowingthe gas to leak through vacuum seal 28 into line 26, and subsequentlyinto drying zone 100. In an alternate embodiment, the inert gas can bedirectly supplied to drying zone 100 through an inert gas inlet (notdepicted). The inert gas can be fed to drying zone 100 at a feed rate ofless than about 5 standard cubic feet of gas per pound of wet cake indrying zone 100 (SCF/lb), less than about 3 SCF/lb, or less than 1SCF/lb. Suitable examples of inert gases useful in the present inventioninclude, but are not limited to, nitrogen and/or air.

In one embodiment of the present invention, drying zone 100 can bedefined within a dryer. In another embodiment, drying zone 100 can bedefined within a contact dryer. As used herein, the term “contact dryer”is defined as a dryer where heat is transferred to the material beingdried (e.g., solid TPA particles) by physically contacting the materialbeing dried with a thermally conductive wall (e.g., a heated innersurface) that separates a heat source (e.g., a heat transfer medium)from the material being dried. In an alternate embodiment, drying zone100 can be defined within a plurality of contact dryers arranged inseries.

FIG. 2 illustrates one embodiment of a contact dryer 102 that can definedrying zone 100. In this embodiment, dryer 102 can comprise asubstantially horizontally disposed elongated tubular cylinder 104presenting an inner surface 106. Furthermore, dryer 102 can comprise ajacket 108 which allows a heat transfer medium to circulatetherethrough. Additionally, dryer 102 can comprise feed inlet 110,product outlet 112, and vapor outlet 118. Optionally, a drying gas inlet120 can also be provided.

In one embodiment of the present invention, cylinder 104 can have alength of less than about 80 feet, less than about 40 feet, or less than20 feet. Additionally, cylinder 104 can have an inner diameter in therange of from about 1 to about 15 feet. Inner surface 106 can have anarea in the range of from about 4 to about 40 square feet (ft²), in therange of from about 6 to about 35 ft², or in the range of from 8 to 30ft².

In one embodiment of the present invention, jacket 108 can substantiallyenvelop cylinder 104, thereby allowing a heat transfer medium tocirculate between the outer surface of cylinder 104 and the innersurface of jacket 108. During drying operations, the heat transfermedium circulating in jacket 108 can operate to transfer heat tocylinder 104. This transfer of heat can raise the temperature of innersurface 106, resulting in a heated inner surface. During dryingoperations, inner surface 106 can have a temperature of at least about100° C., in the range of from about 115 to about 265° C., or in therange of from 200 to 250° C. During drying operations, jacket 108 canhave a temperature in the range of from about 120 to about 280° C., inthe range of from about 160 to about 250° C., or in the range of from200 to 240° C.

Jacket 108 can comprise heat transfer medium inlet 114 and heat transfermedium outlet 116. Heat transfer medium inlet 114 allows for theintroduction of the heat transfer medium into jacket 108, and spent heattransfer medium can be withdrawn via heat transfer medium outlet 116.

The heat transfer medium employed in the present invention can be anymedium sufficient to increase the temperature of inner surface 106 asdiscussed above. In one embodiment, the heat transfer medium can be aliquid and/or a gas. Suitable examples of heat transfer mediums usefulin the present invention include, but are not limited to, steam, water,oil, and/or commercially available natural or synthetic heat transfermedium fluids. The heat transfer medium introduced into jacket 108 canhave an inlet temperature in the range of from about 120 to about 280°C., in the range of from about 160 to about 250° C., or in the range offrom 200 to 240° C. As used herein, when referring to the heat transfermedium, the term “inlet temperature” is defined as being the temperatureof the heat transfer medium immediately upon being introduced intojacket 108. Furthermore, the heat transfer medium can have an outlettemperature in the range of from about 110 to about 270° C., in therange of from about 130 to about 250° C., or in the range of from 150 to240° C. Additionally, the pressure in jacket 108 during dryingoperations can be maintained in the range of from about 50 to about 700pounds per square inch gauge (psig), in the range of from about 70 toabout 650 psig, or in the range of from 90 to 600 psig.

Referring still to FIG. 2, dryer 102 can comprise a paddle rotor 122.Paddle rotor 122 can be disposed substantially coaxially within cylinder104. Paddle rotor 122 can comprise a plurality of radial arms 124.Radial arms 124 can be positioned along the length of paddle rotor 122in a substantially helical pattern. Each of radial arms 124 can comprisea paddle or blade 126 rotatably attached to the end of radial arms 124.Paddles 126 can be adjustably secured to the end of radial arms 124 soas to permit presetting of the pitch of each paddle 126.

FIG. 3 illustrates in detail radial arms 124 and paddles 126. The lengthof radial arms 124 combined with paddles 126 can extend at least about80 percent, at least about 85 percent, or at least 90 percent of thedistance of the annular space created between paddle rotor 122's outersurface 128 and inner surface 106.

Referring again to FIG. 2, at least a portion of the wet cake comprisingthe solid particles as discussed above can be introduced into dryer 102via feed inlet 110. Paddle rotor 122 can be operable to facilitatecontact of the solid particles with inner surface 106 and to facilitatemovement of the solid particles through cylinder 104. To achieve suchcontacting and movement, paddle rotor 122 can rotate so as to impartcentrifugal and axially forward forces on at least a portion of thesolid particles. In one embodiment, the centrifugal force created bypaddle rotor 122 can be sufficient to at least partially overcome theforce of gravity, thereby forming a thin layer of the solid particlesover at least a portion of inner surface 106. In one embodiment, atleast about 10 percent, at least about 40 percent, or at least 70percent of the solid particles introduced into dryer 102 can form a thinlayer over at least a portion of inner surface 106. The centrifugalforce created by paddle rotor 122 can be sufficient to form a thin layerof solid particles over at least about 20 percent, at least about 35percent, or at least 50 percent of inner surface 106. The thin layer ofsolid particles created on inner surface 106 can have an averagethickness of less than about 1.5 inches, less than about 1 inch, or lessthan 0.5 inches.

The axially forward forces created by paddle rotor 122 can be sufficientto transport the solid particles from feed inlet 110 to product outlet112 within the residence times discussed above. Arms 124 and paddles 126can be oriented so that when paddle rotor 122 rotates, the solidparticles follow a substantially helical path from feed inlet 110, alonginner surface 106, to product outlet 112. One example of a substantiallyhelical path the solid particles could follow during drying operationsis depicted by path 130.

In order to achieve the above-mentioned centrifugal and axially forwardforces on the solid particles, paddle rotor 122 can rotate at asufficient speed. The speed of rotation of paddle rotor 122 can bemeasured by determining the speed at which the tips of paddles 126 aretraveling (tip speed) during drying operations. The tip speed of paddles126 during drying operations can be at least about 10 cm/s, in the rangeof from about 20 to about 400 cm/s, in the range of from about 50 toabout 300 cm/s, or in the range of from 100 to 150 cm/s.

At least a portion of the liquid removed from the above-mentioned wetcake during drying operations can be discharged via vapor outlet 118.Vapor discharged from vapor outlet 118 can be treated in substantiallythe same manner as the vapor in line 22 of FIG. 1, discussed above.Vapor outlet 118 can have a diameter that is sufficiently narrow so asto at least partially prevent entrained solids from escaping dryer 102concurrent with removed vapor. In one embodiment, vapor outlet 118 canhave a diameter of less than about 15 feet, less than about 10 feet, orless than 5 feet.

In one embodiment of the present invention, a drying gas may be employedto facilitate at least partial direct-contact drying of the solidparticles in dryer 102. When a drying gas is employed, the drying gascan enter dryer 102 via drying gas inlet 120. The drying gas employed inthe present invention can be any gas capable of removing at least aportion of the liquid from the above-mentioned wet cake. Suitableexamples of drying gases useful in the present invention include, butare not limited to, nitrogen, TPA process off-gases, oxygen-depletedgas, carbon dioxide, carbon monoxide, and/or air. As used herein, theterm “TPA process off-gas” is defined as a gas which was used in theoxidation step of a TPA production process. Optionally, the TPA processoff-gas can be scrubbed and/or treated in a regenerative thermaloxidation unit prior to being employed as a drying gas. As used herein,the term “oxygen-depleted gas” is defined as a gas having less thanabout 7 mol percent oxygen. In one embodiment, the oxygen-depleted gascan have an oxygen content of less than about 5 mol percent, less thanabout 3 mol percent, or less than 1 mol percent.

In one embodiment, the drying gas can have an inlet temperature of atleast about the boiling point of the liquid to be removed from the wetcake. In another embodiment, the drying gas can have an inlettemperature in the range of from about 100 to about 250° C., in therange of from about 120 to about 225° C., or in the range of from 140 to200° C. As used herein, when referring to the drying gas, the term“inlet temperature” is defined as being the temperature of the dryinggas immediately upon being introduced into dryer 102. When a drying gasis employed in dryer 102, the pressure in dryer 102 can be up to about1000 torr during drying operations. The pressure in dryer 102 isdetermined by measuring the pressure at product outlet 112.

As mentioned above, the solid particles can exit dryer 102 via productoutlet 112. In one embodiment of the present invention, theabove-mentioned substantially dry TPA particulate product can compriseat least a portion of the solid particles exiting dryer 102 via productoutlet 112. In another embodiment, the solid particles exiting dryer 102via product outlet 112 can be treated in substantially the same manneras the solid particles in line 26 of FIG. 1, discussed above.

In one embodiment of the present invention, dryer 102 can be a thinlayer contact dryer. As used herein, the term “thin layer contact dryer”is defined as a contact dryer wherein at least a portion of the solidparticles entering the dryer form a layer having an average thickness ofless than about 1.5 inches over at least a portion of the heated innersurface of the dryer. Suitable examples of commercially available thinlayer contact dryers for use in the present invention include, but arenot limited to, a SOLIDAIRE dryer (manufactured by Bepex InternationalLLC, Minneapolis, Minn., USA), or a TURBODRYER (manufactured by VOMMS.P.A., Milan, Italy).

It will be understood by one skilled in the art that each of theabove-described embodiments, as well as any sub-parts of thoseembodiments, may be operated in a continuous or a non-continuous manner.Non-continuous operations include, but are not limited to, batch-wiseoperations, cyclical operations, and/or intermittent operations.

EXAMPLES

The following examples are intended to be illustrative of the presentinvention in order to teach one of ordinary skill in the art to make anduse the invention and are not intended to limit the scope of theinvention in any way.

Example 1 Preparation of PTA Wet Cake

Two batches of PTA wet cake were prepared for use in the examples below.Each batch was prepared by mixing glacial acetic acid with dry PTApowder in a 16 cubic foot ribbon mixer. Batch 1 was prepared by firstadding approximately 600 lbs of dry PTA powder to the ribbon mixer andturning on the agitator. Next, approximately 67 lbs of glacial aceticacid was added over approximately a 1 hour time period. The mixer wasthen allowed to operate for several hours to ensure a substantiallyhomogeneous mixture. Bach 2 was prepared in the same manner as batch 1,except approximately 150 lbs of glacial acetic acid was mixed with the600 lbs of dry PTA powder. After mixing, each batch was analyzed todetermine its moisture content. Batch 1 contained 11 weight percentmoisture and batch 2 contained 18 weight percent moisture.

Example 2 Dryers

Two different classes of dryers were compared in the examples below fortheir efficacy in drying a PTA-containing wet cake. The first class ofdryer used in the examples below was represented by the TORUSDISC TD12-4 dryer (manufactured by Bepex International LLC, Minneapolis, Minn.,USA). The TORUSDISC TD 12-4 dryer is an indirect heat exchanger having aheated dryer area of 27.6 square feet. The TORUSDISC TD 12-4 representsa class of dryers characterized by a single or twin shaft heated rotor,a heated jacket, and slow, gentle movement of solids through the dryerduring drying. Other dryers in this class include the DISCOTHERM-B dryer(manufactured by LIST USA Inc., Charlotte, N.C., USA), the HOLO-FLITEdryer (manufactured by Metso Minerals, Helsinki, Finland), the PORCUPINEprocessor (manufactured by Bethlehem Corp., Easton, Pa., USA), the K-SNARA PADDLE dryer (manufactured by Komline-Sanderson Engineering Corp.,Peapack, N.J., USA), and the ROVACTOR dryer (manufactured byBuss-SMS-Canzler GmbH, Butzbach, Germany).

The second class of dryer used in the examples below was represented bythe SOLIDAIRE dryer (manufactured by Bepex International LLC,Minneapolis, Minn., USA). Two different models of the SOLIDAIRE dryerwere used in the examples below: the SOLIDAIRE SJS 10-6 and theSOLIDAIRE SJS 8-4. The SOLIDAIRE dryers represent a class of dryersknown as thin layer contact dryers, which are characterized by a heatedjacket, a heated inner surface, and a paddle rotor having blades thatcan be angled, shaped, or oriented so as to impart centrifugal andaxially forward forces to the material being dried. The SOLIDAIRE dryersare capable of producing a highly agitated thin layer of cake. Each ofthe SOLIDAIRE dryers employed can be direct and/or indirect heatexchangers. The SJS 10-6 dryer has a heated drying area of 15 squarefeet, and the SJS 8-4 has a heated drying area of 8 square feet. Anotherdryer in this class is the TURBODRYER (manufactured by VOMM S.P.A.,Milan, Italy).

Example 3 Dryer Residence Time

To compare the performance of the dryers described in Example 2, a totalof 4 samples of the PTA wet cake containing 18 weight percent moisture,as prepared in Example 1, were dried in a TORUSDISC TD 12-4 dryer and aSOLIDAIRE SJS 10-6 dryer, two samples in each dryer. In each of the 4runs, the wet cake was metered into the dryer with a screw feeder. Thefeed rate was varied from 27 pounds per hour per square foot of heateddrying area (lbs/hr/ft²) to 93 lbs/hr/ft². A vacuum system was employedduring the drying procedure which removed the acid vapor from the dryer.Additionally, during the drying procedure the dryer was purged withnitrogen. After drying, the dried PTA was removed from the dryers via arotary air lock valve, which allowed the dry powder to be removed fromthe dryer while maintaining a substantially constant level of pressurein the dryer. The dry PTA temperature, the moisture content, and theresidence time of the dried PTA product were then measured. In each ofthe 4 runs, the jacket temperature of the dryer was maintained at 180°C. during drying. The results are listed in Table 1, below.

TABLE 1 Effect of Dryer on Residence Time TORUSDISC SOLIDAIRE TD 12-4SJS 10-6 Run 1 Run 2 Run 3 Run 4 Wet Cake Feed Rate 27 33 40 93(lbs/hr/ft²) Dry PTA Temperature 168 160 160 131 (° C.) Dry PTA Weight0.05 0.09 0.03 0.01 Percent Moisture Dryer Residence Time 7.8 6.5 2.71.7 (min.)

As can be seen by looking at the results listed in Table 1, each of thetwo dryers was able to produce a dry PTA product having less than 0.1weight percent moisture. However, it is clear that the SOLIDAIRE dryerprovides shorter residence times than the TORUSDISC dryer, whileachieving the same or better level of reduction in moisture.

Example 4 Jacket Temperature and Feed Rate

The effect of the jacket temperature and feed rate on dry PTAtemperature, dry PTA weight percent moisture, and dryer residence timewas determined by performing drying operations on five samples of thePTA wet cake containing 11 weight percent moisture, as prepared inExample 1. For this determination, a SOLIDAIRE SJS 8-4 dryer wasemployed. Each sample in turn was metered to the dryer using a screwfeeder. The feed rate for each of the five runs was varied from 75lbs/hr/ft² to 175 lbs/hr/ft². Additionally, the jacket temperature ofthe dryer was varied from 200° C. (Runs 1-3) to 223° C. (Run 4) and 244°C. (Run 5). After drying, the dried PTA was removed from the dryer via arotary air lock valve, which allowed the dry powder to be removed fromthe dryer while maintaining a substantially constant level of pressurein the dryer. The dry PTA temperature, the moisture content, and theresidence time of the dried PTA product were then measured. The resultsare listed in Table 2, below.

TABLE 2 Effect of Jacket Temperature and Feed Rate Dryer JacketTemperature 200° C. 223° C. 244° C. Run 1 Run 2 Run 3 Run 4 Run 5 WetCake Feed Rate 75 113 150 125 175 (lbs/hr/ft²) Dry PTA Temperature 152146 117 154 140 (° C.) Dry PTA Weight Percent 0.11 0.03 1.1 0.09 0.05Moisture Dryer Residence Time 1.6 1.1 0.8 1.0 0.7 (min.)

As can be seen by looking at the results listed in Table 2, the feedrate in Run 3 was increased to 150 lbs/hr/ft² while maintaining a jackettemperature of 200° C. This resulted in a dried PTA product having anunacceptably high level of moisture content (1.1 weight percent).However, as Runs 4 and 5 demonstrate, when the dryer jacket temperatureis increased, the wet cake feed rate can also be increased withouthaving a deleterious effect on the moisture content of the dried PTAproduct.

Example 5 Thermal Stability of Terephthalic Acid

The thermal stability of terephthalic acid (TPA) was determined byperforming thermal gravimetric analysis (TGA) on two samples of crudeterephthalic acid (CTA) and two samples of PTA. One of the PTA samplesand one of the CTA samples was tested in an air environment, while theother two samples were tested in a nitrogen environment. A modifiedversion of ASTM method E1131-03 (Standard Test Method for CompositionalAnalysis by Thermogravimetry) was followed for this example. The methodwas modified by lowering the highest testing temperature to 350° C. Theanalyses were performed on a HI-RES TGA 2950 THERMOGRAVIMETRIC ANALYZER(manufactured by TA Instruments, New Castle, Del., USA). The scan rateemployed in each analysis was 5° C. per minute.

The results from the TGA analysis of TPA are shown in FIGS. 4 and 4 a.FIG. 4 depicts the thermal degradation and/or sublimation ofterephthalic acid over a temperature range starting at 0° C. and endingat 350° C., while FIG. 4 a is a magnified view of FIG. 4, depicting thethermal degradation and/or sublimation of TPA over a temperature rangefrom 185° C. to. 285° C. As can be seen by looking at FIG. 4 a, it isapparent that severe thermal degradation and/or sublimation of the TPAbegins to occur at temperatures greater than about 250° C. Thermaldegradation begins to occur at about 250° C. whether the sample is CTAor PTA, and occurs in both air environments and nitrogen environments.

Numerical Ranges

The present description uses numerical ranges to quantify certainparameters relating to the invention. It should be understood that whennumerical ranges are provided, such ranges are to be construed asproviding literal support for claim limitations that only recite thelower value of the range as well as claims limitation that only recitethe upper value of the range. For example, a disclosed numerical rangeof 10 to 100 provides literal support for a claim reciting “greater than10” (with no upper bounds) and a claim reciting “less than 100” (with nolower bounds).

The present description uses specific numerical values to quantifycertain parameters relating to the invention, where the specificnumerical values are not expressly part of a numerical range. It shouldbe understood that each specific numerical value provided herein is tobe construed as providing literal support for a broad, intermediate, andnarrow range. The broad range associated with each specific numericalvalue is the numerical value plus and minus 60 percent of the numericalvalue, rounded to two significant digits. The intermediate rangeassociated with each specific numerical value is the numerical valueplus and minus 30 percent of the numerical value, rounded to twosignificant digits. The narrow range associated with each specificnumerical value is the numerical value plus and minus 15 percent of thenumerical value, rounded to two significant digits. For example, if thespecification describes a specific temperature of 62° F., such adescription provides literal support for a broad numerical range of 25°F. to 99° F. (62° F.+/−37° F.), an intermediate numerical range of 43°F. to 81° F. (62° F.+/−19° F.), and a narrow numerical range of 53° F.to 71° F. (62° F.+/−9° F.). These broad, intermediate, and narrownumerical ranges should be applied not only to the specific values, butshould also be applied to differences between these specific values.Thus, if the specification describes a first pressure of 110 psia and asecond pressure of 48 psia (a difference of 62 psi), the broad,intermediate, and narrow ranges for the pressure difference betweenthese two streams would be 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi,respectively.

Definitions

As used herein, the terms “comprising,” “comprises,” and “comprise” areopen-ended transition terms used to transition from a subject recitedbefore the term to one or more elements recited after the term, wherethe element or elements listed after the transition term are notnecessarily the only elements that make up the subject.

As used herein, the terms “including,” “includes,” and “include” havethe same open-ended meaning as “comprising,” “comprises,” and“comprise.”

As used herein, the terms “having,” “has,” and “have” have the sameopen-ended meaning as “comprising,” “comprises,” and “comprise.”

As used herein, the terms “containing,” “contains,” and “contain” havethe same open-ended meaning as “comprising,” “comprises,” and“comprise.”

As used herein, the terms “a,” “an,” “the,” and “said” mean one or more.

As used herein, the term “and/or,” when used in a list of two or moreitems, means that any one of the listed items can be employed by itselfor any combination of two or more of the listed items can be employed.For example, if a composition is described as containing components A,B, and/or C, the composition can contain A alone; B alone; C alone; Aand B in combination; A and C in combination; B and C in combination; orA, B, and C in combination.

Claims Not Limited to Disclosed Embodiments

The forms of the invention described above are to be used asillustration only, and should not be used in a limiting sense tointerpret the scope of the present invention. Obvious modifications tothe exemplary embodiments, set forth above, could be readily made bythose skilled in the art without departing from the spirit of thepresent invention.

The inventors hereby state their intent to rely on the Doctrine ofEquivalents to determine and assess the reasonably fair scope of thepresent invention as pertains to any apparatus not materially departingfrom but outside the literal scope of the invention as set forth in thefollowing claims.

1. A method for drying solid particles comprising an aromaticdicarboxylic acid and a liquid, comprising: (a) introducing a wet cakecomprising the solid aromatic dicarboxylic acid particles and at leastone liquid into a thin layer contact dryer comprising a heated innersurface and a paddle rotor which imparts centrifugal and axially forwardforce to the wet cake; (b) forming a layer of wet cake of at least 10%of the solid particles having an average thickness of less than 1.5inches over at least a portion of the heated inner surface and (c)removing the liquid from the solid particles of the aromaticdicarboxylic acid to thereby produce substantially dry aromaticdicarboxylic acid particles, wherein the at least one liquid comprisesat least one of water and acetic acid, the wet cake comprises from about2 to about 25 weight percent liquid, a feed rate of the wet cake to thethin layer contact dryer is at least about 20 lbs/hour per square footof heated surface area of the thin layer contact dryer, an averageresidence time of the solid particles in the thin layer contact dryer isless than about 7 minutes, a temperature of the particles in the thinlayer contact dryer does not exceed a temperature of sublimation orthermal degradation according to thermogravimetric analysis of thearomatic dicarboxylic acid, an exit temperature of the solid particlesfrom the thin layer contact dryer is less than about 250° C. and the drysolid aromatic dicarboxylic acid particles comprise less than about 1weight percent of the liquid.
 2. The method of claim 1, wherein theaverage residence time is less than about 5 minutes.
 3. The method ofclaim 1, wherein at least about 40 percent of the solid particles form alayer over at least a portion of the inner surface, wherein the layer isless than about 1 inch thick.
 4. The method of claim 1, wherein the exittemperature is from about 105 to about 240° C.
 5. The method of claim 1,wherein a feed rate of the wet cake to the thin layer contact dryer isfrom about 40 to about 175 lbs/hour per square foot of heated surfacearea of the thin layer contact dryer.
 6. The method of claim 1, whereina temperature of the wet cake is from about 20 to 120° C. immediatelyprior to entering the thin layer contact dryer.
 7. The method of claim1, wherein the substantially dry aromatic dicarboxylic acid particlescomprise less than about 0.5 weight percent liquid.
 8. The method ofclaim 1, wherein the aromatic dicarboxylic acid is terephthalic acid. 9.The method of claim 8, wherein the terephthalic acid is crudeterephthalic acid.
 10. The method of claim 1, wherein the thin layercontact dryer comprises a jacketed cylinder providing the heated innersurface.
 11. The method of claim 10, wherein a temperature of the heatedinner surface is maintained from about 120 to about 280° C.
 12. Themethod of claim 10, wherein the thin layer contact dryer furthercomprises a paddle rotor disposed substantially coaxially within thejacketed cylinder.
 13. The method of claim 12, wherein the paddle rotorcomprises a plurality of radial arms extending from the rotor.
 14. Themethod of claim 13, wherein each of the radial arms comprises a paddlethat is rotatable relative to the radial arms.
 15. The method of claim13, wherein the arms and the paddles extend at least about 80 percent ofa distance of an annular space between the outer surface of the paddlerotor and the heated inner surface.
 16. The method of claim 13, whereinthe radial arms form a substantially helical pattern along a length ofthe paddle rotor.
 17. The method of claim 10, wherein the jacket allowsfor a heat transfer medium to be circulated there through, wherein theheat transfer medium comprises a fluid.
 18. The method of claim 17,wherein the jacket comprises a heat transfer medium inlet forintroducing the heat transfer medium into the jacket, wherein the heattransfer medium has an inlet temperature of from about 120 to about 280°C.
 19. The method of claim 12, wherein the paddle rotor facilitates bothcontact of the solid particles with the heated inner surface andmovement of the solid particles through the jacketed cylinder.
 20. Themethod of claim 19, wherein a layer of the solid particles forms over atleast about 20 percent of the heated inner surface.
 21. The method ofclaim 14, wherein the tips of the paddles travel at a speed of at leastabout 10 cm/s.
 22. The method of claim 10, wherein a temperature of theheated surface is from about 115 to about 265° C.
 23. The method ofclaim 1, further comprising introducing a drying gas into the thin layercontact dryer, wherein an inlet temperature of the drying gas is atleast about 100° C.
 24. The method of claim 1, wherein the thin layercontact dryer comprises an inert atmosphere.
 25. The method of claim 1,wherein the thin layer contact dryer further comprises a vacuum sealdevice through which the solid aromatic dicarboxylic acid particles exitthe dryer.
 26. The method of claim 25, wherein the vacuum seal devicecomprises a rotary air lock valve.
 27. A method for producing asubstantially dry crude terephthalic acid (CTA) particulate product,comprising: (a) oxidizing an aromatic compound in an oxidation zone tothereby produce a slurry comprising solid CTA particles; (b) treating atleast a portion of the slurry in a product isolation zone to therebyproduce a wet cake comprising solid CTA particles; and (c) drying thewet cake in a thin layer contact dryer comprising a heated inner surfaceto thereby produce the substantially dry CTA particulate product,wherein the at least one liquid comprises at least one of water andacetic acid, the wet cake comprises from about 2 to about 25 weightpercent liquid, a feed rate of the wet cake to the thin layer contactdryer is at least about 20 lbs/hour per square foot of heated surfacearea of the thin layer contact dryer, at least about 10 percent of thesolid CTA particles form a layer having an average thickness of lessthan about 1.5 inches over at least a portion of the inner surface, anaverage residence time of the CTA particles in the thin layer contactdryer is less than about 7 minutes, an exit temperature of the solid CTAparticles is less than about 250° C., and the dry solid CTA particlescomprise less than about 1 weight percent of the liquid.
 28. The methodof claim 27, wherein the average residence time is less than about 5minutes.
 29. The method of claim 27, wherein the substantially dry CTAparticulate product comprises less than about 2 weight percent liquid.30. The method of claim 27, wherein the exit temperature is from about105 to about 240° C.
 31. The method of claim 27, further comprisingcreating a vacuum in the product isolation zone and the drying zoneduring the drying with a common vacuum source.
 32. The method of claim27, wherein the thin layer contact dryer comprises: a jacketed cylinderproviding the heated inner surface, and a paddle rotor disposedsubstantially coaxially within the jacketed cylinder.
 33. The method ofclaim 32, wherein the paddle rotor comprises a plurality of radial armsextending from the rotor, wherein each of the radial arms comprises apaddle that is rotatable relative to the radial arms.
 34. The method ofclaim 32, wherein the jacket comprises a heat transfer medium inlet forintroducing a heat transfer medium into the jacket, wherein an inlettemperature of the heat transfer medium is from about 120 to about 280°C.
 35. The method of claim 32, wherein the paddle rotor facilitates bothcontact of the solid CTA particles with the heated inner surface andmovement of the solid particles through the jacketed cylinder.
 36. Amethod for producing a substantially dry purified terephthalic acid(PTA) particulate product, comprising: (a) oxidizing an aromaticcompound in an oxidation zone to thereby produce a first slurrycomprising solid crude terephthalic acid (CTA) particles; (b) subjectingat least a portion of the CTA particles to purification in apurification zone to thereby produce a second slurry comprising solidPTA particles; (c) treating at least a portion of the second slurry in aproduct isolation zone to thereby produce a wet cake comprising the PTAparticles; and (d) drying the wet cake in a thin layer contact dryer tothereby produce the substantially dry PTA particulate product, whereinthe wet cake comprises from about 2 to about 25 weight percent liquid,the liquid comprises at least one of water and acetic acid, a feed rateof the wet cake to the thin layer contact dryer is at least about 20lbs/hour per square foot of heated surface area of the thin layercontact dryer, at least about 10 percent of the solid PTA particles forma layer having an average thickness of less than about 1.5 inches overat least a portion of the inner surface, an average residence time ofthe PTA particles in the thin layer contact dryer is less than about 7minutes, and an exit temperature of the solid PTA particles is less thanabout 250° C. and the dry solid PTA particles comprise less than about 1weight percent of the liquid.
 37. The method of claim 36, wherein theaverage residence time is less than about 5 minutes.
 38. The method ofclaim 36, wherein the substantially dry PTA particles comprise less thanabout 1 weight percent liquids.
 39. The method of claim 36, wherein theexit temperature is from about 105 to about 240° C.
 40. The method ofclaim 36, further comprising creating a vacuum in the product isolationzone and the drying zone during the drying with a common vacuum source.41. The method of claim 36, wherein the thin layer contact dryercomprises: a jacketed cylinder providing the heated inner surface, and apaddle rotor disposed substantially coaxially within the jacketedcylinder.
 42. The method of claim 41, wherein the jacket comprises aheat transfer medium inlet for introducing a heat transfer medium intothe jacket, wherein an inlet temperature of the heat transfer medium isfrom about 120 to about 280° C.
 43. The method of claim 41 wherein thepaddle rotor comprises a plurality of radial arms extending from therotor, wherein each of the radial arms comprises a paddle that isrotatable relative to the radial arms.
 44. The method of claim 41,wherein the paddle rotor facilitates both contact of the solid particleswith the heated inner surface and movement of the solid particlesthrough the jacketed cylinder.
 45. A method for drying a wet cakecomprising terephthalic acid (TPA), comprising: (a) introducing the wetcake into a thin layer contact dryer; and (b) drying the wet cake insaid dryer to thereby produce a dry TPA product, wherein the wet cakecomprises from about 2 to about 25 weight percent liquid, the liquidcomprises at least one of water and acetic acid, a feed rate of the wetcake to the thin layer contact dryer is at least about 20 lbs/hour persquare foot of heated surface area of the thin layer contact dryer, atleast a portion of the TPA in the wet cake forms a thin layer on theinside surface of the dryer, and a temperature of the dry TPA exitingfrom the dryer is from about 105 to about 240° C., and the dry solid TPAparticles comprise less than about 1 weight percent of the liquid. 46.The method of claim 45, wherein an average residence time of the TPA inthe thin layer contact dryer is less than about 7 minutes.
 47. Themethod of claim 45, wherein a temperature of the dry TPA product exitingthe thin layer dryer is from about 125 to about 200° C.
 48. The methodof claim 45, wherein the dry TPA product comprises less than 1 weightpercent liquid.
 49. The method of claim 45, wherein the thin layercontact dryer comprises a jacketed cylinder having a heated innersurface.
 50. The method of claim 49, wherein a feed rate of the wet caketo the thin layer dryer is at least about 35 lbs/hour per square foot ofthe heated inner surface.
 51. The method of claim 49, wherein the thinlayer contact dryer further comprises a paddle rotor having a pluralityof blades.
 52. The method of claim 51, wherein at least a portion of theblades impart centrifugal and axially forward forces on the TPA.
 53. Themethod of claim 49, wherein a temperature of the inner surface of thethin layer contact dryer is from about 120 to about 270° C.
 54. A methodfor drying a wet cake comprising terephthalic acid (TPA), said methodcomprising: (a) introducing the wet cake into a dryer, wherein the dryercomprises a thin layer contact dryer having a heated inner surface and ajacket, wherein the jacket temperature of the dryer is maintained in therange of from about 120 to about 270° C., wherein at least about 10percent of the solid particles form a layer over at least a portion ofthe inner surface, wherein the layer has an average thickness of lessthan about 1.5 inches and wherein the wet cake is fed to the dryer at afeed rate of at least about 35 lbs/hour per square foot of the heatedinner surface during the drying; and (b) drying the wet cake in thedryer to thereby produce a dry TPA product, wherein said TPA has anaverage residence time in the dryer of from about 1 minute to about 5minutes, and wherein the dry TPA product has a temperature in the rangeof from about 105 to about 240° C. upon exiting the dryer, wherein thewet cake comprises from about 2 to about 25 weight percent liquid, theliquid comprises at least one of water and acetic acid, and the dry TPAproduct comprises less than about 1 weight percent of the liquid. 55.The method of claim 54, wherein the TPA has an average residence time inthe dryer of from about 1 minute to about 3 minutes.
 56. The method ofclaim 54, wherein the dry TPA product has less than about 0.1 weightpercent moisture.